Organic catalyst with enhanced enzyme compatibility

ABSTRACT

This invention relates to cleaning compositions comprising organic catalysts having enhanced enzyme compatibility and processes for making and using such cleaning compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of and claims priority under 35U.S.C. §120 to U.S. patent application Ser. No. 12/468,907 filed May 20,2009, which is a continuation of and claims priority under 35 U.S.C.§120 to U.S. patent application Ser. No. 11/272,276 filed Nov. 10, 2005,which in turn claims priority under 35 U.S.C. §119(e) to U.S.Provisional Application Ser. No. 60/691,621 filed Jun. 17, 2005, and isa continuation-in-part of and claims priority under 35 U.S.C. §120 toU.S. patent application Ser. No. 10/447,506 filed May 29, 2003, which inturn claims priority under 35 U.S.C. §119(e) to U.S. ProvisionalApplication Ser. No. 60/386,692 filed Jun. 6, 2002, and U.S. ProvisionalApplication Ser. No. 60/426,549 filed Nov. 15, 2002.

FIELD OF INVENTION

This invention relates to cleaning compositions comprising organiccatalysts and processes for making and using such cleaning products.

BACKGROUND OF THE INVENTION

Oxygen bleaching agents, for example hydrogen peroxide, are typicallyused to facilitate the removal of stains and soils from clothing andvarious surfaces. Unfortunately such agents are extremely temperaturerate dependent. As a result, when such agents are employed in coldersolutions, the bleaching action of such solutions is markedly decreased.

In an effort to resolve the aforementioned performance problem, theindustry developed a class of materials known as “bleach activators”.However, as such materials rapidly lose their effectiveness at solutiontemperatures of less than 40° C., new organic catalysts such as3,4-dihydro-2-[2-(sulfooxy)decyl]isoquinolimium, inner salt weredeveloped. In general, while such current art catalysts are effective inlower temperature water conditions, they can inactivate certain enzymes.As most laundry and cleaning compositions are formulated with enzymes,formulating cleaning products with such catalysts can be problematic.

Accordingly, there is a need for an inexpensive cleaning compositioncomprising an organic catalyst that can provide the combined benefits offormulation flexibility, low water temperature bleaching performance andenzyme compatibility.

SUMMARY OF THE INVENTION

The present invention relates to cleaning compositions comprisingorganic catalysts having enhanced enzyme compatibility, and methods ofmaking and using same.

DETAILED DESCRIPTION OF THE INVENTION Definitions

As used herein, the term “cleaning composition” includes, unlessotherwise indicated, granular or powder-form all-purpose or “heavy-duty”washing agents, especially laundry detergents; liquid, gel or paste-formall-purpose washing agents, especially the so-called heavy-duty liquidtypes; liquid fine-fabric detergents; hand dishwashing agents or lightduty dishwashing agents, especially those of the high-foaming type;machine dishwashing agents, including the various tablet, granular,liquid and rinse-aid types for household and institutional use; liquidcleaning and disinfecting agents, including antibacterial hand-washtypes, laundry bars, mouthwashes, denture cleaners, car or carpetshampoos, bathroom cleaners; hair shampoos and hair-rinses; shower gelsand foam baths and metal cleaners; as well as cleaning auxiliaries suchas bleach additives and “stain-stick” or pre-treat types.

As used herein, the phrase “is independently selected from the groupconsisting of . . . ” means that moieties or elements that are selectedfrom the referenced Markush group can be the same, can be different orany mixture of elements.

The test methods disclosed in the Test Methods Section of the presentapplication must be used to determine the respective values of theparameters of Applicants' inventions.

Unless otherwise noted, all component or composition levels are inreference to the active level of that component or composition, and areexclusive of impurities, for example, residual solvents or by-products,which may be present in commercially available sources.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

All documents cited are, in relevant part, incorporated herein byreference; the citation of any document is not to be construed as anadmission that it is prior art with respect to the present invention.

Cleaning Compositions Comprising Organic Catalyst

Applicants have found that judicious selection of the R¹ moiety of theorganic catalyst of the present invention results in improved enzymecompatibility. While not being bound by theory, Applicants believe thisis due to favorable partitioning of the catalyst in aqueous environmentsas a result of the aforementioned judicious selection of the R¹ moiety.

In one aspect of Applicants' invention, Applicants' cleaningcompositions comprise an organic catalyst having an enzyme compatibilityvalue of 70 or greater, or even 80 or greater.

In one aspect of Applicants' invention, Applicants' cleaningcompositions comprise an organic catalyst having Formula 1 or Formula 2below or mixtures thereof.

wherein R₁ is a branched alkyl group containing from 9 to 24 carbons orlinear alkyl group containing from 11 to 24 carbons; a branched alkylgroup containing from 9 to 18 carbons or linear alkyl group containingfrom 11 to 18 carbons; is selected from the group consisting of2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl,n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl,iso-tridecyl and iso-pentadecyl; or is selected from the groupconsisting of 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, iso-tridecyland iso-pentadecyl.

The balance of any aspects of the aforementioned cleaning compositionsis made up of one or more adjunct materials.

Processes of Making Suitable Organic Catalysts

Suitable organic catalysts can be produced using a variety of reactionvessels and processes including batch, semi-batch and continuousprocesses.

In one aspect of Applicants invention, the process of making theaforementioned catalyst comprises the step of reacting3,4-dihydroisoquinoline sulfur trioxide complex with an epoxide to formsaid organic catalyst.

In another aspect of Applicants' invention, the process of making theaforementioned catalyst comprises the steps of reacting3,4-dihydroisoquinoline with a material selected from the groupconsisting of sulfur trioxide, a material that provides sulfur trioxideand mixtures thereof, to form a 3,4-dihydroisoquinoline sulfur trioxidecomplex, and reacting such 3,4-dihydroisoquinoline sulfur trioxidecomplex with an epoxide to form said organic catalyst.

In another aspect of Applicants' invention, the process of making theaforementioned catalyst comprises the step of reacting3,4-dihydroisoquinoline with an epoxide sulfur trioxide complex to formsaid organic catalyst.

In another aspect of Applicants' invention, the process of making theaforementioned catalyst comprises the steps of reacting an epoxide witha material selected from the group consisting of sulfur trioxide, amaterial that provides sulfur trioxide and mixtures thereof, to form anepoxide sulfur trioxide complex, and reacting such epoxide sulfurtrioxide complex with 3,4-dihydroisoquinoline to form said organiccatalyst.

The oxaziridinium ring containing version of the aforementioned catalystmay be produced by contacting an iminium ring containing version of saidcatalyst with an oxygen transfer agent such as a peroxycarboxylic acidor a peroxymonosulfuric acid, for example, Oxone®. Such species can beformed in situ and used without purification.

While the skilled artisan who processes the teachings of thisspecification can easily determine the desired reaction conditions andreactant concentrations, typical reaction parameters for theaforementioned aspects of Applicants' invention include reactiontemperatures of from about 0° C. to about 150° C., or from about 0° C.to about 125° C., reaction pressures of from about 0.1 to about 100atmospheres, from about 0.3 atmospheres to about 10 atmospheres or fromabout 1 atmosphere to about 10 atmospheres; reaction times of 0.1 hoursto about 96 hours, from about 1 hour to about 72 hours, or from about 1hour to about 24 hours. The reaction may also be run under an inertatmosphere or otherwise anhydrous conditions including, when a solventis employed, the use of an anhydrous solvent.

Materials that are employed in practicing Applicants' process include3,4-dihydroisoquinoline; epoxides and mixtures thereof; sulfur trioxide,sources of sulfur trioxide and mixtures thereof; and solvents.

When 3,4-dihydroisoquinoline is employed, the initial reaction mixturetypically comprises from about 0.5 weight % to about 70 weight %, fromabout 5 weight % to about 70 weight %, or from about 10 weight % toabout 50 weight % of such material. 3,4-Dihydroisoquinoline can be madeaccording to the protocol found in Example 1.

When epoxides are employed, the initial reaction mixture typicallycomprises from about 0.5 weight % to about 70 weight %, from about 5weight % to about 70 weight %, or from about 10 weight % to about 50weight % of such material. Suitable epoxides include but are not limitedto epoxides such as 2-propylheptyl glycidyl ether; 2-butyloctyl glycidylether; 2-pentylnonyl glycidyl ether; 2-hexyldecyl glycidyl ether;n-dodecyl glycidyl ether; n-tetradecyl glycidyl ether; n-hexadecylglycidyl ether; n-octadecyl glycidyl ether; iso-nonyl glycidyl ether;iso-decyl glycidyl ether; iso-tridecyl glycidyl ether, and mixturesthereof. Such materials may contain oligomeric forms of the glycidylether which may optionally be removed prior to being employed as areactant. 2-Propylheptyl glycidyl ether can be prepared as described inExample 2 of this specification. All of the other aforementionedglycidyl ethers can be prepared by following the generic protocol ofExample 2 by substituting the appropriate alcohol in place of2-propylheptanol. Suitable alcohols include 2-propylheptanol,2-butyloctanol, 2-pentylnonanol, 2-hexyldecanol, n-dodecanol,n-tetradecanol, n-hexadecanol, n-octadecanol, iso-nonanol, iso-decanoland iso-tridecanol.

When sulfur trioxide, sources of sulfur trioxide and mixtures thereofare employed, the initial reaction mixture typically comprises fromabout 0.5 weight % to about 70 weight %, from about 5 weight % to about70 weight %, or from about 10 weight % to about 50 weight % of suchmaterial. Suitable materials include sulfur trioxide, and sulfurtrioxide complexes such as sulfur trioxide trimethylamine, sulfurtrioxide dioxane, sulfur trioxide pyridine, sulfur trioxideN,N-dimethylformamide, sulfur trioxide sulfolane, sulfur trioxidetetrahydrofuran, sulfur trioxide diethylether, sulfur trioxide3,4-dyhydroisoquinoline and mixtures thereof.

The balance of any reaction mixture is typically solvent. When a solventis employed, the initial reaction mixture typically comprises up to 99weight % solvent, from about 10 weight % to about 90 weight % solvent,or from about 20 weight % to about 80 weight % solvent. Suitablesolvents include aprotic, polar and apolar solvents such as acetonitile,dioxane, tertbutyl methylether, tetrahydrofuran, N,N-dimethylformamide,sulfolane, chlorobenzene, toluene, 1,2-dichloroethane, methylenechloride, chloroform, diethyl ether, hexanes, pentanes, benzene, xylenesand mixtures thereof. Suitable solvents can be purchased from Aldrich,P.O. Box 2060, Milwaukee, Wis. 53201, USA.

Cleaning Compositions and Cleaning Composition Additives ComprisingApplicants' Organic Catalysts

The cleaning composition of the present invention may be advantageouslyemployed for example, in laundry applications, hard surface cleaning,automatic dishwashing applications, as well as cosmetic applicationssuch as dentures, teeth, hair and skin. However, due to the uniqueadvantages of both increased effectiveness in lower temperaturesolutions and the superior enzyme compatibility, the organic catalystsof the present invention are ideally suited for laundry applicationssuch as the bleaching of fabrics through the use of bleach containingdetergents or laundry bleach additives. Furthermore, the organiccatalysts of the present invention may be employed in both granular andliquid compositions.

The organic catalysts of the present invention may also be employed in acleaning additive product. A cleaning additive product including theorganic catalysts of the present invention is ideally suited forinclusion in a wash process when additional bleaching effectiveness isdesired. Such instances may include but, are not limited to, lowtemperature solution cleaning application. The additive product may be,in its simplest form, Applicants' organic catalyst. Preferably, theadditive could be packaged in dosage form for addition to a cleaningprocess where a source of peroxygen is employed and increased bleachingeffectiveness is desired. Such single dosage form may comprise a pill,tablet, gelcap or other single dosage unit such as pre-measured powdersor liquids. A filler or carrier material may be included to increase thevolume of such composition. Suitable filler or carrier materialsinclude, but are not limited to, various salts of sulfate, carbonate andsilicate as well as talc, clay and the like. Filler or carrier materialsfor liquid compositions may be water or low molecular weight primary andsecondary alcohols including polyols and diols. Examples of suchalcohols include, but are not limited to, methanol, ethanol, propanoland isopropanol. The compositions may contain from about 5% to about 90%of such materials. Acidic fillers can be used to reduce pH.Alternatively, the cleaning additive may include an activated peroxygensource defined below or the adjunct ingredients as fully defined below.

Applicants' cleaning compositions and cleaning additives require acatalytically effective amount of Applicants' organic catalyst. Therequired level of such catalyst may be achieved by the addition of oneor more species of Applicants' organic catalyst. As a practical matter,and not by way of limitation, the compositions and cleaning processesherein can be adjusted to provide on the order of at least 0.001 ppm,from about 0.001 ppm to about 500 ppm, from about 0.005 ppm to about 150ppm, or even from about 0.05 ppm to about 50 ppm of Applicants' organiccatalyst in the wash liquor. In order to obtain such levels in the washliquor, typical compositions herein may comprise from about 0.0002% toabout 5%, or even from about 0.001% to about 1.5%, of organic catalyst,by weight of the cleaning compositions.

When the Applicants' organic catalyst is employed in a granularcomposition, it may be desirable for the Applicants' organic catalyst tobe in the form of an encapsulated particle to protect the Applicants'organic catalyst from moisture and/or other components of the granularcomposition during storage. In addition, encapsulation is also a meansof controlling the availability of the Applicants' organic catalystduring the cleaning process and may enhance the bleaching performance ofthe Applicants' organic catalyst. In this regard, the Applicants'organic catalyst can be encapsulated with any encapsulating materialknown in the art.

The encapsulating material typically encapsulates at least part,preferably all, of the Applicants' organic catalyst. Typically, theencapsulating material is water-soluble and/or water-dispersible. Theencapsulating material may have a glass transition temperature (Tg) of0° C. or higher.

The encapsulating material is preferably selected from the groupconsisting of carbohydrates, natural or synthetic gums, chitin andchitosan, cellulose and cellulose derivatives, silicates, phosphates,borates, polyvinyl alcohol, polyethylene glycol, paraffin waxes andcombinations thereof. Preferably the encapsulating material is acarbohydrate, typically selected from the group consisting ofmonosaccharides, oligosaccharides, polysaccharides, and combinationsthereof. Most preferably, the encapsulating material is a starch.Preferred starches are described in EP 0 922 499; U.S. Pat. No.4,977,252; U.S. Pat. No. 5,354,559 and U.S. Pat. No. 5,935,826.

The encapsulating material may be a microsphere made from plastic suchas thermoplastics, acrylonitrile, methacrylonitrile, polyacrylonitrile,polymethacrylonitrile and mixtures thereof; commercially availablemicrospheres that can be used are those supplied by Expancel ofStockviksverken, Sweden under the trademark Expancel®, and thosesupplied by PQ Corp. of Valley Forge, Pa. USA under the tradename PM6545, PM 6550, PM 7220, PM 7228, Extendospheres®, Luxsil®, Q-cel® andSphericel®.

The cleaning compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, or even about 7.5 and 10.5.Liquid dishwashing product formulations may have a pH between about 6.8and about 9.0. Laundry products typically have a pH of from about 9 toabout 11. Techniques for controlling pH at recommended usage levelsinclude the use of buffers, alkalis, acids, etc., and are well known tothose skilled in the art.

Adjunct Materials

While not essential for the purposes of the present invention, thenon-limiting list of adjuncts illustrated hereinafter are suitable foruse in the instant compositions and may be desirably incorporated incertain embodiments of the invention, for example to assist or enhancecleaning performance, for treatment of the substrate to be cleaned, orto modify the aesthetics of the cleaning composition as is the case withperfumes, colorants, dyes or the like. The precise nature of theseadditional components, and levels of incorporation thereof, will dependon the physical form of the composition and the nature of the cleaningoperation for which it is to be used. Suitable adjunct materialsinclude, but are not limited to, surfactants, builders, chelatingagents, dye transfer inhibiting agents, dispersants, enzymes, and enzymestabilizers, catalytic materials, bleach activators, hydrogen peroxide,sources of hydrogen peroxide, preformed peracids, polymeric dispersingagents, clay soil removal/anti-redeposition agents, brighteners, sudssuppressors, dyes, perfumes, structure elasticizing agents, fabricsofteners, carriers, hydrotropes, processing aids, solvents and/orpigments. In addition to the disclosure below, suitable examples of suchother adjuncts and levels of use are found in U.S. Pat. Nos. 5,576,282,6,306,812 B1 and 6,326,348 B1 that are incorporated by reference.

As stated, the adjunct ingredients are not essential to Applicants'compositions. Thus, certain embodiments of Applicants' compositions donot contain one or more of the following adjuncts materials:surfactants, builders, chelating agents, dye transfer inhibiting agents,dispersants, enzymes, and enzyme stabilizers, catalytic materials,bleach activators, hydrogen peroxide, sources of hydrogen peroxide,preformed peracids, polymeric dispersing agents, clay soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,perfumes, structure elasticizing agents, fabric softeners, carriers,hydrotropes, processing aids, solvents and/or pigments. However, whenone or more adjuncts are present, such one or more adjuncts may bepresent as detailed below:

Bleaching Agents—The cleaning compositions of the present invention maycomprise one or more bleaching agents. Suitable bleaching agents otherthan bleaching catalysts include photobleaches, bleach activators,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof. In general, when a bleaching agent is used, thecompositions of the present invention may comprise from about 0.1% toabout 50% or even from about 0.1% to about 25% bleaching agent by weightof the subject cleaning composition. Examples of suitable bleachingagents include:

(1) photobleaches for example sulfonated zinc phthalocyanine;

(2) preformed peracids: Suitable preformed peracids include, but are notlimited to, compounds selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, for example,Oxzone®, and mixtures thereof. Suitable percarboxylic acids includehydrophobic and hydrophilic peracids having the formula R—(C═O)O—O-Mwherein R is an alkyl group, optionally branched, having, when theperacid is hydrophobic, from 6 to 14 carbon atoms, or from 8 to 12carbon atoms and, when the peracid is hydrophilic, less than 6 carbonatoms or even less than 4 carbon atoms; and M is a counterion, forexample, sodium, potassium or hydrogen;

(3) sources of hydrogen peroxide, for example, inorganic perhydratesalts, including alkali metal salts such as sodium salts of perborate(usually mono- or tetra-hydrate), percarbonate, persulphate,perphosphate, persilicate salts and mixtures thereof. In one aspect ofthe invention the inorganic perhydrate salts are selected from the groupconsisting of sodium salts of perborate, percarbonate and mixturesthereof. When employed, inorganic perhydrate salts are typically presentin amounts of from 0.05 to 40 wt %, or 1 to 30 wt % of the overallcomposition and are typically incorporated into such compositions as acrystalline solid that may be coated. Suitable coatings include,inorganic salts such as alkali metal silicate, carbonate or borate saltsor mixtures thereof, or organic materials such as water-soluble ordispersible polymers, waxes, oils or fatty soaps; and

(4) bleach activators having R—(C═O)-L wherein R is an alkyl group,optionally branched, having, when the bleach activator is hydrophobic,from 6 to 14 carbon atoms, or from 8 to 12 carbon atoms and, when thebleach activator is hydrophilic, less than 6 carbon atoms or even lessthan 4 carbon atoms; and L is leaving group. Examples of suitableleaving groups are benzoic acid and derivatives thereof—especiallybenzene sulphonate. Suitable bleach activators include dodecanoyloxybenzene sulphonate, decanoyl oxybenzene sulphonate, decanoyloxybenzoic acid or salts thereof, 3,5,5-trimethyl hexanoyloxybenzenesulphonate, tetraacetyl ethylene diamine (TAED) and nonanoyloxybenzenesulphonate (NOBS). Suitable bleach activators are also disclosed in WO98/17767. While any suitable bleach activator may be employed, in oneaspect of the invention the subject cleaning composition may compriseNOBS, TAED or mixtures thereof.

When present, the peracid and/or bleach activator is generally presentin the composition in an amount of from about 0.1 to about 60 wt %, fromabout 0.5 to about 40 wt % or even from about 0.6 to about 10 wt % basedon the composition. One or more hydrophobic peracids or precursorsthereof may be used in combination with one or more hydrophilic peracidor precursor thereof.

The amounts of hydrogen peroxide source and peracid or bleach activatormay be selected such that the molar ratio of available oxygen (from theperoxide source) to peracid is from 1:1 to 35:1, or even 2:1 to 10:1.

Surfactants—The cleaning compositions according to the present inventionmay comprise a surfactant or surfactant system wherein the surfactantcan be selected from nonionic surfactants, anionic surfactants, cationicsurfactants, ampholytic surfactants, zwitterionic surfactants,semi-polar nonionic surfactants and mixtures thereof. When present,surfactant is typically present at a level of from about 0.1% to about60%, from about 1% to about 50% or even from about 5% to about 40% byweight of the subject composition.

Builders—The cleaning compositions of the present invention may compriseone or more detergent builders or builder systems. When a builder isused, the subject composition will typically comprise at least about 1%,from about 5% to about 60% or even from about 10% to about 40% builderby weight of the subject composition.

Builders include, but are not limited to, the alkali metal, ammonium andalkanolammonium salts of polyphosphates, alkali metal silicates,alkaline earth and alkali metal carbonates, aluminosilicate builders andpolycarboxylate compounds, ether hydroxypolycarboxylates, copolymers ofmaleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, thevarious alkali metal, ammonium and substituted ammonium salts ofpolyacetic acids such as ethylenediamine tetraacetic acid andnitrilotriacetic acid, as well as polycarboxylates such as melliticacid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid,benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, andsoluble salts thereof.

Chelating Agents—The cleaning compositions herein may contain achelating agent. Suitable chelating agents include copper, iron and/ormanganese chelating agents and mixtures thereof. When a chelating agentis used, the subject composition may comprise from about 0.005% to about15% or even from about 3.0% to about 10% chelating agent by weight ofthe subject composition.

Dye Transfer Inhibiting Agents—The cleaning compositions of the presentinvention may also include one or more dye transfer inhibiting agents.Suitable polymeric dye transfer inhibiting agents include, but are notlimited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Whenpresent in a subject composition, the dye transfer inhibiting agents maybe present at levels from about 0.0001% to about 10%, from about 0.01%to about 5% or even from about 0.1% to about 3% by weight of thecomposition.

Brighteners—The cleaning compositions of the present invention can alsocontain additional components that may tint articles being cleaned, suchas fluorescent brighteners. Suitable fluorescent brightener levelsinclude lower levels of from about 0.01, from about 0.05, from about 0.1or even from about 0.2 wt % to upper levels of 0.5 or even 0.75 wt %.

Dispersants—The compositions of the present invention can also containdispersants. Suitable water-soluble organic materials include the homo-or co-polymeric acids or their salts, in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other bynot more than two carbon atoms.

Enzymes—The cleaning compositions can comprise one or more enzymes whichprovide cleaning performance and/or fabric care benefits. Examples ofsuitable enzymes include, but are not limited to, hemicellulases,peroxidases, proteases, cellulases, xylanases, lipases, phospholipases,esterases, cutinases, pectinases, mannanases, pectate lyases,keratinases, reductases, oxidases, phenoloxidases, lipoxygenases,ligninases, pullulanases, tannases, pentosanases, malanases,β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase,and amylases, or mixtures thereof. A typical combination is an enzymecocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in a cleaning composition, theaforementioned enzymes may be present at levels from about 0.00001% toabout 2%, from about 0.0001% to about 1% or even from about 0.001% toabout 0.5% enzyme protein by weight of the composition.

Enzyme Stabilizers—Enzymes for use in detergents can be stabilized byvarious techniques. The enzymes employed herein can be stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions that provide such ions to the enzymes. In caseof aqueous compositions comprising protease, a reversible proteaseinhibitor, such as a boron compound, can be added to further improvestability.

Catalytic Metal Complexes—Applicants' cleaning compositions may includecatalytic metal complexes. One type of metal-containing bleach catalystis a catalyst system comprising a transition metal cation of definedbleach catalytic activity, such as copper, iron, titanium, ruthenium,tungsten, molybdenum, or manganese cations, an auxiliary metal cationhaving little or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282.

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. No. 5,597,936; U.S. Pat. No. 5,595,967. Suchcobalt catalysts are readily prepared by known procedures, such astaught for example in U.S. Pat. No. 5,597,936, and U.S. Pat. No.5,595,967.

Compositions herein may also suitably include a transition metal complexof ligands such as bispidones (WO 05/042532 A1) and/or macropolycyclicrigid ligands—abbreviated as “MRLs”. As a practical matter, and not byway of limitation, the compositions and processes herein can be adjustedto provide on the order of at least one part per hundred million of theactive MRL species in the aqueous washing medium, and will typicallyprovide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm toabout 10 ppm, or even from about 0.1 ppm to about 5 ppm, of the MRL inthe wash liquor.

Suitable transition-metals in the instant transition-metal bleachcatalyst include, for example, manganese, iron and chromium. SuitableMRLs include 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane.

Suitable transition metal MRLs are readily prepared by known procedures,such as taught for example in WO 00/32601, and U.S. Pat. No. 6,225,464.

Solvents—Suitable solvents include water and other solvents such aslipophilic fluids. Examples of suitable lipophilic fluids includesiloxanes, other silicones, hydrocarbons, glycol ethers, glycerinederivatives such as glycerine ethers, perfluorinated amines,perfluorinated and hydrofluoroether solvents, low-volatilitynonfluorinated organic solvents, diol solvents, otherenvironmentally-friendly solvents and mixtures thereof.

Processes of Making Cleaning and/or Treatment Compositions

The cleaning compositions of the present invention can be formulatedinto any suitable form and prepared by any process chosen by theformulator, non-limiting examples of which are described in Applicants'examples and in U.S. Pat. No. 5,879,584; U.S. Pat. No. 5,691,297; U.S.Pat. No. 5,574,005; U.S. Pat. No. 5,569,645; U.S. Pat. No. 5,565,422;U.S. Pat. No. 5,516,448; U.S. Pat. No. 5,489,392; U.S. Pat. No.5,486,303 all of which are incorporated herein by reference.

Method of Use

The present invention includes a method for cleaning a situs inter aliaa surface or fabric. Such method includes the steps of contacting anembodiment of Applicants' cleaning composition, in neat form or dilutedin a wash liquor, with at least a portion of a surface or fabric thenoptionally rinsing such surface or fabric. The surface or fabric may besubjected to a washing step prior to the aforementioned rinsing step.For purposes of the present invention, washing includes but is notlimited to, scrubbing, and mechanical agitation. As will be appreciatedby one skilled in the art, the cleaning compositions of the presentinvention are ideally suited for use in laundry applications.Accordingly, the present invention includes a method for laundering afabric. The method comprises the steps of contacting a fabric to belaundered with a said cleaning laundry solution comprising at least oneembodiment of Applicants' cleaning composition, cleaning additive ormixture thereof. The fabric may comprise most any fabric capable ofbeing laundered in normal consumer use conditions. The solutionpreferably has a pH of from about 8 to about 10.5. The compositions maybe employed at concentrations of from about 500 ppm to about 15,000 ppmin solution. The water temperatures typically range from about 5° C. toabout 90° C. The water to fabric ratio is typically from about 1:1 toabout 30:1.

Organic Catalyst/Enzyme Compatibility Test

The test described below uses an alpha amylase activity assay to measurethe impact of organic catalysts on the enzyme.

Equipment. UV/Vis spectrophotometer capable of measuring @ 415 nm,heated magnetic stirrer capable of 40° C., 5 mL Luer lock syringe andfilters (Acrodisc 0.45 μm), pH meter, and balance (4-place analytical).

Reagents. Merck Amylase Kit (Merck Eurolab, Cat. No. 1.19718.0001);Trizma Base (Sigma Cat # T-1503, or equivalent); Calcium ChlorideDihydrate (Sigma Cat # C-5080, or equivalent); Sodium ThiosulfatePentahydrate (Sigma Cat # S-6672 or equivalent); Hydrochloric Acid (VWRCat # JT9535-0, or equivalent); Hardness solution (CTC Group, 3.00 gr/ccor equivalent); Sodium Percarbonate; Peracetic Acid (Aldrich, Cat.#26933-6 or equivalent); Amylase enzymes: Termamyl, Natalase, and Duramyl(Novozymes, Denmark); Granular detergent matrix containing no enzyme,organic catalyst or bleaching agents.

1.) Solution Preparation: prepare the following:

-   -   a.) TRIS Assay Buffer. Prepare 1 liter of 0.1M TRIS buffer, 0.5%        sodium thiosulphate (W/V), 0.11% calcium chloride (w/v) at pH        8.3.    -   b.) Blank Detergent Solution. Prepare one liter of 0.5% enzyme        and bleach free granular detergent product in deionized water        (W/V) that is 250 ppm H₂O₂ (0.77 gm percarbonate) and 10 gpg        hardness (880 Ul of hardness).    -   c.) Termamyl, Duramyl and Natalase Stock. Make 100 mL solutions        each of a 0.1633 mg active Termamyl per mL TRIS Buffer, a 0.1159        mg active Natalase per mL TRIS Buffer, and a 0.1596 mg active        Duramyl per mL TRIS Buffer.    -   d.) Organic catalyst stocks. Make a 500 ppm in methanol solution        of μm.    -   e.) Peracetic acid stock. Make a 3955 ppm peracetic acid        solution in deionized water.    -   f.) Amylase reagent. Follow Merck kit instructions for preparing        flacons (containers) 1 and 2 using flacon 3 and subsequent        mixing of flacons 1 and 2 to produce the final reagent used in        the amylase activity analysis.

2.) Sample Analysis

-   -   a.) Analysis of sample with enzyme only: Add 100 mL of blank        detergent solution to a 150 mL beaker. Place beaker on heated        stir plate and bring temperature to 40° C. with stirring. Add Y        μL of enzyme stock to the beaker where Y=612 μL for Duramyl, 306        μL for Termamyl, or 918 μL for Natalase. Spike only enzyme of        interest. Stir sample for 1 minute. Start timer. At 7 minutes 45        seconds, pull a sample and filter it using a 0.45 μm syringe        filter (5 mL syringe). Mix 6 μL of filtered sample with 250 μL        of amylase reagent in a cuvette and place the cuvette in a        UV/VIS spectrophotometer and monitor change in absorbance at 415        nm. Determine length of time (t_(E)) to the nearest second        required to obtain an absorbance reading of 1.0 for each enzyme.        Use each enzyme's t_(E) in Steps 2.)b.) and 2.)c.) below.    -   b.) Analysis of sample with enzyme and peracetic acid only.        Follow Step 2.)a.) except after enzyme addition, allow solution        to stir for 1 minute then add 127 μL of peracetic acid stock and        start timer. Pull sample at 7 minutes 45 seconds as in Step        2.)a.). Once sample and reagent are mixed, record the absorbance        at t_(E) for the respective enzyme. Designate such absorbance        A_(b).    -   c.) Analysis of sample with enzyme, peracetic acid, and organic        catalyst. Follow Step 2.)a.) except after enzyme addition, allow        solution to stir for 1 minute then add 127 μL of peracetic acid        stock and 100 μL of organic catalyst stock and start timer. Pull        sample at 7 minutes 45 seconds as in Step 2.)a.). Once sample        and reagent are mixed, record the absorbance at t_(E) for the        respective enzyme. Designate such absorbance A.

3.) Calculate Enzyme Compatibility Value (ECV)

-   -   a.) Calculate the ECV for each specific enzyme: termamyl        (ECV_(ter)), duramyl (ECV_(dur)) and natalase (ECV_(nat)). The        ECV for any specific enzyme is (A_(c)/A_(b))×100 where A_(b) and        A_(c) are the values determined in Steps 2.)b.) and 2.)c.),        respectively, for that enzyme.    -   b.) The ECV for a given organic catalyst is the average of the        individual ECV values for the three enzymes. Thus,        ECV=(ECV_(ter)+ECV_(dur)+ECV_(nat))/3.

EXAMPLES

Unless otherwise indicated, materials can be obtained from Aldrich, P.O.Box 2060, Milwaukee, Wis. 53201, USA. In Examples 1-12, the solventacetonitrile may be replaced with other solvents, including but notlimited to, 1,2-dichloroethane.

Example 1 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-propylheptyloxymethyl)-ethyl]ester,internal salt

Preparation of 2-propylheptyl glycidyl ether: To a flame dried, 500 mLround bottomed flask equipped with an addition funnel charged withepichlorohydrin (15.62 gm., 0.17 moles), is added 2-propylheptanol(Pfaltz & Bauer, Inc., 172 E. Aurora Street, Waterbury Conn., 06708,USA) (20 gm., 0.127 moles) and stannic chloride (0.20 gm., 0.001 moles).The reaction is kept under an argon atmosphere and warmed to 90° C.using an oil bath. Epichlorohydrin is dripped into the stirring solutionover 60 minutes followed by stirring at 90° C. for 18 hours. Thereaction is fitted with a vacuum distillation head and1-chloro-3-(2-propyl-heptyloxy)-propan-2-ol is distilled at atemperature range of 90° C.->95° C. under 0.2 mm Hg. Wt.=22.1 gm. The1-chloro-3-(2-propyl-heptyloxy)-propan-2-ol (5.0 gm., 0.020 moles) isdissolved in tetrahydrofuran (50 mL) and stirred at RT under an argonatmosphere. To the stirring solution is added potassium tert-butoxide(2.52 gm., 0.022 moles) and the suspension is stirred at RT for 18hours. The reaction is then evaporated to dryness, residue dissolved inhexanes and washed with water (100 mL). The hexanes phase is separated,dried with Na₂SO₄, filtered and evaporated to dryness to yield the crude2-propylheptyl glycidyl ether, which can be further purified by vacuumdistillation.

Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-propylheptyloxymethyl)-ethyl]ester,internal salt: To a flame dried 250 mL three neck round bottomed flask,equipped with a condenser, dry argon inlet, magnetic stir bar,thermometer, and heating bath is added 3,4-dihydroisoquinoline (0.38mol.; prepared as described in Example I of U.S. Pat. No. 5,576,282),2-propylheptyl glycidyl ether (0.38 mol, prepared as described above),SO₃-DMF complex (0.38 mol), and acetonitrile (500 mL). The reaction iswarmed to 80° C. and stirred at temperature for 72 hours. The reactionis cooled to room temperature, evaporated to dryness and the residuerecrystallized from ethyl acetate and/or ethanol to yield the desiredproduct.

Example 2 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-butyl-octyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substituting2-butyloctanol for 2-propylheptanol.

Example 3 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-pentyl-nonyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substituting2-pentylnonanol (obtained from Pfaltz & Bauer, Inc., Wayerbury, Conn.06708) for 2-propylheptanol.

Example 4 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(2-hexyl-decyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substituting2-hexyldecanol for 2-propylheptanol.

Example 5 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(dodecyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingn-dodecanol for 2-propylheptanol.

Example 6 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(tetradecyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingn-tetradecanol for 2-propylheptanol.

Example 7 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(hexadecyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingn-hexadecanol for 2-propylheptanol.

Example 8 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(octadecyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingn-octadecanol for 2-propylheptanol.

Example 9 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(iso-nonyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingiso-nonanol (Exxal 9 obtained from Exxon Mobile Chemical, Houston, Tex.USA) for 2-propylheptanol.

Example 10 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(iso-decyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingiso-decanol (obtained from City Chemicals LLC, West Haven, Conn. USA)for 2-propylheptanol.

Example 11 Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(iso-tridecyloxymethyl)-ethyl]ester,internal salt

The desired product is prepared according to Example 1, substitutingiso-tridecanol (obtained from BASF Corporation, Mount Olive, N.J. USA)for 2-propylheptanol.

Example 12 Simultaneous Preparation of Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(iso-tridecyloxymethyl)-ethyl]ester,internal salt and Sulfuric acidmono-[2-(3,4-dihydro-isoquinolin-2-yl)-1-(iso-pentadecyloxymethyl)-ethyl]ester,internal salt

The desired products are prepared according to Example 1, substituting amixture of isomeric tridecanols to pentadecanols (obtained from BASFCorporation, Mount Olive, N.J. USA) for 2-propylheptanol.

Example 13

Bleaching detergent compositions having the form of granular laundrydetergents are exemplified by the following formulations.

A B C D E F Linear alkylbenzenesulfonate 20 22 20 15 20 20 C₁₂Dimethylhydroxyethyl 0.7 1 1 0.6 0.0 0.7 ammonium chloride AE3S 0.9 0.00.9 0.0 0.0 0.9 AE7 0.0 0.5 0.0 1 3 1 sodium tripolyphosphate 23 30 2317 12 23 Zeolite A 0.0 0.0 0.0 0.0 10 0.0 1.6R Silicate 7 7 7 7 7 7Sodium Carbonate 15 14 15 18 15 15 Polyacrylate MW 4500 1 0.0 1 1 1.5 1Carboxy Methyl Cellulose 1 1 1 1 1 1 Savinase 32.89 mg/g 0.1 0.07 0.10.1 0.1 0.1 Natalase 8.65 mg/g 0.1 0.1 0.1 0.0 0.1 0.1 Brightener 150.06 0.0 0.06 0.18 0.06 0.06 Brightener 49 0.1 0.06 0.1 0.0 0.1 0.1Diethylenetriamine 0.6 0.3 0.6 0.25 0.6 0.6 pentacetic acid MgSO₄ 1 1 10.5 1 1 Sodium Percarbonate 0.0 5.2 0.1 0.0 0.0 0.0 Photobleach 0.00300.0015 0.0015 0.0020 0.0045 0.0010 Sodium Perborate Monohydrate 4.4 0.03.85 2.09 0.78 3.63 NOBS 1.9 0.0 1.66 1.77 0.33 0.75 TAED 0.58 1.2 0.510.0 0.015 0.28 Organic Catalyst* 0.0185 0.0185 0.0162 0.0162 0.01110.0074 Sulfate/Moisture Balance to Balance to Balance to Balance toBalance to Balance to 100% 100% 100% 100% 100% 100% *Organic catalystprepared according to Examples 1 through 12, or mixtures thereof. Any ofthe above compositions is used to launder fabrics at a concentration of3500 ppm in water, 25° C., and a 25:1 water:cloth ratio. The typical pHis about 10 but can be can be adjusted by altering the proportion ofacid to Na-salt form of alkylbenzenesulfonate.

Example 14

Bleaching detergent compositions having the form of granular laundrydetergents are exemplified by the following formulations.

A B C D Linear alkylbenzenesulfonate 8 7.1 7 6.5 AE3S 0 4.8 0 5.2Alkylsulfate 1 0 1 0 AE7 2.2 0 3.2 0.1 C₁₀₋₁₂ Dimethyl hydroxy- 0.750.94 0.98 0.98 ethylammonium chloride Crystalline layered silicate 4.1 04.8 0 (δ-Na₂Si₂O₅) Zeolite A 20 0 17 0 Citric Acid 3 5 3 4 SodiumCarbonate 15 20 14 20 Silicate 2R (SiO₂:Na₂O 0.08 0 0.11 0 at ratio 2:1)Soil release agent 0.75 0.72 0.71 0.72 Acrylic Acid/Maleic 1.1 3.7 1.03.7 Acid Copolymer Carboxymethylcellulose 0.15 1.4 0.2 1.4 Protease(56.00 mg active/g) 0.37 0.4 0.4 0.4 Amylase (21.55 mg active/g) 0.3 0.30.3 0.3 Lipase (11.00 mg active/g) 0 0.7 0 0.7 Tetraacetyl ethylene 3.64.0 3.6 4.0 diamine (TAED) Percarbonate 13 13.2 13 13.2 OrganicCatalyst* 0.04 0.02 0.01 0.06 Na salt of Ethylenediamine- 0.2 0.2 0.20.2 N,N′-disuccinic acid, (S,S) isomer (EDDS) Hydroxyethane 0.2 0.2 0.20.2 di phosphonate (HEDP) MgSO₄ 0.42 0.42 0.42 0.42 Perfume 0.5 0.6 0.50.6 Suds suppressor agglomerate 0.05 0.1 0.05 0.1 Soap 0.45 0.45 0.450.45 Sodium sulfate 22 33 24 30 Sulphonated zinc 0.07 0.12 0.07 0.12phtalocyanine Photobleach 0.0014 0.002 0.0014 0.001 Speckles 0.03 0.050.03 0.05 Balance Balance Balance Balance to 100% to 100% to to Water &Miscellaneous 100% 100% * Organic catalyst prepared according toExamples 1 through 12, or mixtures thereof. Any of the abovecompositions is used to launder fabrics at a concentration of 10,000 ppmin water, 20-90° C., and a 5:1 water:cloth ratio. The typical pH isabout 10 but can be can be adjusted by altering the proportion of acidto Na-salt form of alkylbenzenesulfonate.

Example 15

Bleaching detergent compositions having the form of granular laundrydetergents are exemplified by the following formulations.

A B C D E F Linear Alkylbenzenesulfonate 19.0 15.0 20.0 19.0 18.0 17.5Alkylsulfate 1.1 1.0 0.8 1.0 1.1 1.2 AE3S 0.3 0.2 0.0 0.1 0.3 0.5Polyacrylic Acid, partially 6.0 5.5 7.5 7.0 5.8 6.0 neutralized SodiumXylene Sulfonate* 1.5 1.9 2.0 1.7 1.5 1.0 PEG 4000 0.3 0.25 0.35 0.150.2 0.10 Brightener 49 0 0 0.32 0.04 0.04 0.16 Brightener 15 0 0 0.680.08 0.08 0.32 Moisture 2.50 2.00 2.90 2.20 2.40 1.80 Sodium carbonate20.0 17.5 21.0 20.2 19.0 18.0 Sodium Sulfate 0.20 0.30 0.50 0.30 0.450.10 Sodium Silicate 0.25 0.25 0.55 0.30 0.25 0.10 Layered SilicateBuilder 2.7 3.0 2.2 3.7 1.5 1.0 Zeolite A 11.0 11.0 12.5 10.2 9.5 8.0Protease 0.20 0.50 1.0 0.15 0.40 0.0 Silicone Suds Suppressor 0.40 0.351.00 0.60 0.50 0.00 Coarse Sulfate 21.5 23.0 21.0 21.0 20.0 18.5 AmineReaction Product 0.40 0.25 0.10 0.35 0.60 0.00 comprisingδ-Damascone**** Perfume 0.10 0.30 0.20 0.20 0.40 0.50 SodiumPercarbonate 2.8 4.5 2.00 4.7 7.4 10.0 Conventional Activator (NOBS)2.10 3.7 1.00 3.0 5.0 10.0 Organic Catalyst** 0.005 0.10 1.00 0.25 0.050.05 Bluing agent*** 0.50 0.20 1.00 0.30 0.10 0.00 Filler BalanceBalance Balance Balance Balance Balance to to to to to to 100% 100% 100%100% 100% 100% *Other hydrotropes, such as sodium toluenesulfonate, mayalso be used. **Organic catalyst prepared according to Examples 1through 12, or mixtures thereof. ***Such as Ultramarine Blue orAzo-CM-Cellulose (Megazyme, Bray, Co. Wicklow, Ireland) ****Preparedaccording to WO 00/02991.

Any of the above compositions is used to launder fabrics at aconcentration of 500-1500 ppm in water, 5-25° C., and a 15:1-25:1water:cloth ratio. The typical pH is about 9.5-10 but can be can beadjusted by altering the proportion of acid to Na— salt form ofalkylbenzenesulfonate.

Example 16

The organic catalysts listed below are tested according to Applicants'Organic Catalyst/Enzyme Compatibility Test using [Peracetic Acid]=5.0ppm; [organic catalyst]=0.5 ppm and the following results are obtained.

Catalyst Moiety Enzyme Compatibility Values Entry* R¹ ECV_(ter)ECV_(dur) ECV_(nat) ECV 1 tert-butyl 51 86 58 65 2 2-ethylhexyl 54 90 5767 3 2-propylheptyl 98 101 99 99 4 2-butyloctyl 101 101 102 101 5n-C_(12/14) 102 100 100 101 6 iso-nonyl 86 96 88 90 7 iso-decyl 98 97 9697 8 iso-tridecyl 99 100 101 100 *Entries 1 and 2 are respectively C₄and C₈ branched alkyl moieties which are not encompassed by Applicants'Formula 1.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A cleaning composition comprising an organic catalyst having anenzyme compatibility value of 70 or greater and one or more adjunctingredients.
 2. The cleaning composition of claim 1 comprising anorganic catalyst having an enzyme compatibility value of 80 or greater,said composition comprising the following adjunct ingredients: anactivated peroxygen source, an enzyme and a surfactant.
 3. A process ofcleaning a surface or fabric comprising the steps of contacting saidsurface or fabric with a cleaning composition comprising: a.) an organiccatalyst selected from the group consisting of organic catalysts havingthe following formulae: (i)

(iii) and mixtures thereof;

wherein each R¹ is independently a branched alkyl group containing from9 to 24 carbons or linear alkyl group containing from 11 to 24 carbons;and b.) one or more adjunct ingredients; then optionally washing and/orrinsing said surface or fabric.
 4. A process of cleaning a surface orfabric comprising the steps of contacting said surface or fabric withthe cleaning composition of claim 3 wherein R¹ is selected from thegroup consisting of 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl,iso-tridecyl and iso-pentadecyl, said composition comprising thefollowing adjunct ingredients: an activated peroxygen source, an enzymeand a surfactant, then optionally washing and/or rinsing said surface orfabric.